See discussions, stats, and author profiles for this publication at: https://www.researchgate.

net/publication/286286329

Colloid Zirconia Binder of Improved Wetting Properties

Article in Ceramics - Silikaty · March 2012

CITATIONS READS

0 147

5 authors, including:

Maria Morga Zbigniew Adamczyk

Polish Academy of Sciences Akademickie Centrum Komputerowe CYFRONET AGH
42 PUBLICATIONS 705 CITATIONS 264 PUBLICATIONS 8,160 CITATIONS

SEE PROFILE SEE PROFILE

Małgorzata Nattich-Rak Grow Para

Instytut Katalizy i Fizykochemii Powierzchni im. Jerzego Habera, Polskiej Akademi… Rangsit University
49 PUBLICATIONS 999 CITATIONS 27 PUBLICATIONS 712 CITATIONS

SEE PROFILE SEE PROFILE

Some of the authors of this publication are also working on these related projects:

Functional Nano- and Microparticles, Synthesis and Applications in Innovative Materials and Technologies View project

From a single molecule to smart material - understanding the polypeptide complexes formation and properties View project

All content following this page was uploaded by Maria Morga on 11 April 2018.

The user has requested enhancement of the downloaded file.

 Original papers

Colloid Zirconia Binder

of Improved Wetting Properties
#
Maria Morga, Zbigniew Adamczyk, Katarzyna Jaszczółt*,
Małgorzata Nattich-Rak, Grażyna Para

Jerzy Haber Institute of Catalysis and Surface Chemistry,

Polish Academy of Sciences, ul. Niezapominajek 8, 30-239 Cracow, Poland
*Foundry Research Institute, ul. Zakopianska 73, 30-418, Cracow, Poland

#
E-mail: ncmorga@cyf-kr.edu.pl

Submitted September 14, 2011; accepted December 29, 2011

Keywords: Colloid zirconia binder, Density of zirconia binder, Viscosity measurements of zirconia suspensions, Surface
tension of zirconia binders, Wettability of zirconia binder

Physicochemical properties of colloid zirconia aqueous sol, used as a binder in the investment casting industry, were
thoroughly determined. The size of the particles was determined by dynamic light scattering, and the zeta potential of the
particles was measured by microelectrophoresis. The average size of the particles was 13 nm and the zeta potential was
positive, equal to 30 mV. The size distribution of particles deposited on mica surface was also determined using AFM
measurements. The wetting properties of the binder suspension were determined for the paraffin/air interface using the shape
analysis of pendant and sessile drops. The perfluorononanoic acid (PFNA), an anionic surfactant, the non-ionic fluorinated
surfactants Zonyl FSO-100 and Rokafenol RN8, and the mixtures of the surfactants were studied. Our investigations showed
that the Zonyl-FSO surfactant and its mixture with Rokafenol effectively reduced the dynamic contact angle from the initial
value of 94° to the value of 30°. Such low contact angles represent an essential improvement of zirconia binder wettability,
thus widen the range of applicability in investment casting of finely shaped details.

Introduction The interfacial tension of liquid/liquid or liquid/gas

Zirconia (zirconium dioxide, ZrO2) finds
many applications in various fields of industry. Its
physicochemical properties make it very useful in
optical coatings [1, 2], thermal-shield, corrosion
resistant coatings, fuel cells, catalyst and advanced
ceramics [2, 3]. In some technological processes the
addition of nanostructured ZrO2 improves the resistance
to temperature [4], making it useful for the preparation
of high-quality titanium casts in the precise investment
casting industry [2, 5].
Understanding and quantitative description of rheo-
logical behavior of colloidal suspensions is of great
importance in the analysis and control of the properties
of ceramic materials for the investment casting industry
where colloidal sols are used as binders for producing
casting forms [6]. Stability of the suspensions, the
absence of aggregation processes and high fluidity is
vital for producing ceramics of complex geometrical
shape with a defect-free microstructure after sintering
[7-10]. Rheological measurements are of fundamental
interest because of the information that can be derived
from them about the structure of the colloid suspension
and the specific interaction among particles [11].
Ceramics – Silikáty 56 (1) 1-8 (2012)
interfaces exerts an essential influence on the kinetics
of many technological processes [12]. The decrease of
the interfacial tension determines also the wettability of
solid substrates by liquids, which has a major practical
significance. For example, in the case of fine pattern
details, which are the most difficult to be well-wetted
by unmodified binders, the efficient wetting of wax
patterns by ceramic slurries produced from zirconium
binders is critical for the investment casting industry in
order to reduce the number of faulty parts. Therefore,
various surfactants, especially of a non-ionic character,
are added to improve the wetting properties of binders
and slurries. The modification of wetting properties of
suspensions is not trivial because of a large specific
surface area which may lead to a partial removal of
surfactants due to the adsorption on solid particles.
Despite the major significance of these problems, few
systematic studies have been carried out in the literature
based on quantitative measurements of surface tension
and the contact angles of binders on various interfaces.
In our previous work [12] the case of colloid silica
modifications using surfactant mixtures was studied.
Therefore, the primary aim of this work was to
develop efficient methods for a quantitative charac-
1
 Morga M., Adamczyk Z., Jaszczółt K., Nattich-Rak M., Para G.
terization of wetting properties of zirconium binders used
in the investment casting industry. These methods are
based on combined measurements of surface tension and
the dynamic contact angles using drop shape analysis.
In this way an optimum composition and concentration
range of surfactants can be specified, enabling essential
improvements of wetting properties of binders. Other
methods described in this paper are also of great
importance to predict the behavior of colloidal particles,
and consequently, the stability of the suspension [13,
14].
Experimental
Materials
In our experimental studies the following surfactants
were used:
- perfluorononanonic acid CF3(CF2)7COOH, having a
purity of 97% (Aldrich), average molecular weight
of 464 (hereafter referred to as PFNA, an anionic
surfactant),
- Zonyl FSO-100 (C2H4O)x(CF2)yC2H5FO (Aldrich), ave-
rage molecular weight of 726, a non-ionic surfactant,
- Rokafenol RN8 (produced by Rokita, Dolny Brzeg,
Poland), which is a mixture of compounds synthesized
by the nonylphenol/ethylene oxide polycondensation
reaction with a number of (–O–CH2–CH2–) groups
ranging from 6 to 9, average molecular weight of 616,
a non-ionic surfactant.
As a binder the following colloidal zircon-based
product was used:
- Zircon IV oxide, ZrO2 - 20 %, a colloidal dispersion
(Nyacol).
Data given by the manufacturer:
- solid content in stock solution 20% [w/v], pH = 3.5,
density ρ = 1.26 g cm-3.
Other materials:
- as a model wax pattern substrate, the parafilm of “M’’,
Laboratory Film, American National Can™ was used.
- as a substrate for zirconia colloidal particles deposition,
ruby mica sheets supplied by Continental Trade Ltd.
Poland were used. Thin mica sheets were freshly
cleaved and used in experiments without any pre-
treatment.
Experimental methods and procedures
The surface tension and contact
angle measurements
The surface tension and contact angle measurements
were carried out using the drop shape analysis method
presented schematically in Figure 1. The home-made
2 Ceramics – Silikáty 56 (1) 1-8 (2012)
apparatus exploits the video image processing system
of a pendant drop for surface tension measurements,
and the sessile drop for contact angle measurements.
This method enables one to perform non-stationary
(dynamic) surface tension measurements of surfactants
over long periods of time, sometimes hours, which is
especially vital in the case of diluted surfactant solu-
tion, where the surface tension varies slowly with time
due to the diffusion of surfactants to the liquid/air
interface. This set-up enables one to perform direct mea-
surements of the dynamic surface tension of binders
modified by surfactants and, simultaneously, the dyna-
mic contact angle under the same temperature and
humidity conditions. In order to determine contact
angles, the stalagmometer was placed over the paraffin
surface. The only change in the set-up is the substitution
of the container with the examined solution onto the
table covered with a wax film. A pendant drop, which
was detached from the capillary and formed a sessile
drop at the paraffin surface, is characterized by the
advancing contact angle ϑ. The volume of sessile drops
was constant, equal to 20 µl. The computer software
allowed one to determine the contact angle every 5 sec.
In order to increase the precision of measurements, the
whole set-up was situated on an anti-vibration table.
In this work at least five kinetic measurements of
contact angles and surface tension were done for each
experimental condition. The relative error for contact
angle measurements was +/- 2°. The surface tension and
contact angle measurements were carried out at 295 K.
The principle of this method described in detail in
previous works [15-17], is based on producing the drop
and determining its shape on the basis of computer image
analysis. Images of the drop are taken by a video camera
equipped with a macro lens. The images are digitized
in real time by a Matrox Meteor frame grabber card
installed in a personal computer. The image processing
is done in C++ using the commercial software library Mil-
Lite 4.0 by Matrox.
Figure 1. The scheme of the experimental apparatus used for
simultaneous surface tension and contact angle measurements
(1 - stalagmometer, 2 - quartz capillary, 3 - investigated
solution, 4 - thermostatic chamber, 5 - camera, 6 - computer,
7 - light source).
 Colloid zirconia binder of improved wetting properties
The density and dynamic
viscosity measurements
The zirconia concentration in the suspension was
determined by the densitometer, providing relatively
precise measurements of 5×10-6. The measurements
were carried out using the Anton Paar densitometer. This
method is based on an oscillating U-shaped capillary
and may be used for measurements of density and
concentration.
The density of the stock zirconia suspension ρs
and the supernatant solution ρe were measured using
this device. Then, the weight fraction of zirconia in the
suspension was determined from the formula [7, 11].
ρ p ( ρ s − ρe )
wp = (1)
ρ s ( ρ p − ρe )
where ρp = 2.0 g cm-3 is the specific density of zirconia
particles for the weight fraction equal to 0.33.
The density of the zirconia powder after roasting
was determined by a pycnometer. The dynamic viscosity
measurements were carried out using the commercial
Schott ViscoClack device, thermostated at a temperature
of 293 K. The stock sample of the zirconia binder was
diluted by acetic acid solutions keeping a fixed pH value.
The volume fraction of the solid was calculated from
the formula Φv = (wp · ρsus)/ρc, where wp is the weight
fraction solid in the diluted binder determined from the
mass balance, ρsus is the suspension density determined
by the densitometer and ρc is the solid zirconia particle
density.
The particle size and zeta
potential measurements
Diffusion coefficients and the electrophoretic mobi-
lity of zirconia nanoparticles were determined using a
Zetasizer Nano ZS Malvern instrument (measurement
range of 3 nm to 10 μm for zeta potential and 0.6 nm
to 6 μm for particle size). The size of colloidal particles
was determined by the dynamic light scattering (DLS)
method. From the autocorrelation function, the diffusion
coefficient D of zirconia nanoparticles can be easily
calculated, and knowing D one can calculate the hydro-
dynamic radius of particles RH from the Stokes-Einstein
relationship [18, 19]:
kT
RH = (2)
6πη D
where k is the Boltzmann constant, T is the absolute
temperature, η is the viscosity of the solution, and RH
is the hydrodynamic radius of particles.
It is important to mention that in the case of nearly
spherical particles, the hydrodynamic radius corresponds
to the geometrical radius of the particle a.
On the other hand, the zeta potential of zirconia
particles ζ was measured in the same device exploiting
Ceramics – Silikáty 56 (1) 1-8 (2012)
laser Doppler velocimetry (LDV). The principle of this
method consists in the fact that charged particles are
attracted to the oppositely charged electrode and their
velocity is measured and expressed per unit field strength
as the electrophoretic mobility µe. Knowing the mobility,
one can calculate the zeta potential of particles using the
Henry-Smoluchowski equation [20,21]:
3η
ζ = µe (3)
2ε F (κ a )
where ε is the dielectric constant of the zirconia disper-
sion, F(κa) is the function of the dimensionless κa para-
meter, κ-1 = (εkT/2e2I)1/2 is the double-layer thickness,
e the elementary charge, I = 1/2(Σi ci zi2) is the ionic
strength of the electrolyte, ci are the ion concentrations
in the bulk, and zi are the ion valences.
Additionally, the zirconia binder size distribution
was determined by depositing the particles on a mica
substrate under diffusion-controlled conditions. Then,
the atomic force microscopy (AFM) method was applied
using the NT MDT Integra device to acquire particle
monolayer topology. Using image analysis software, the
average horizontal diameter of the deposited particles
was determined for approx. 100 particles and the average
particle size was determined.
Results and discussion
The zeta potential and the particle
size measurements
One of the most important characteristics of colloi-
dal binders is the zeta potential and particle size, which
were determined via microelectro-phoretic and DLS
measurements. Zeta potential, which is strictly correlated
with the uncompensated surface charge of particles [20,
21], determines the stability of colloid suspensions and
interaction of particles with surfaces leading to deposition
phenomena. Knowing the zeta potential of suspensions,
one can quantitatively predict their stability, i.e., their
tendency to form aggregates [18, 22], which usually
diminishes the techno-logical properties of colloidal
binders. It was determined that the zeta potential of the
zirconia binder was positive, varying between 33 and 26
mV for the ionic strength of 10-4 M – 10-2 M (pH = 4.1).
On the other hand, the particle size in the sus-
pension was determined by measuring the diffusion
coefficient using DLS. From these measurements,
using Eq.(2) it was found that the average size of the
particles, assumed equal to 2 RH, was 13 nm +/- 3nm
(see Table 1). This is above the value given by the
manufacturer, equal to 5-10 nm. In order to clarify this
discrepancy, zirconia particle size was also determined
via AFM measurements of particles deposited on mica.
The use of mica is advantageous because molecularly
smooth sheets can be easily cleaved having a macroscopic
dimension. Mica is also negatively charged for all pH
3
 Morga M., Adamczyk Z., Jaszczółt K., Nattich-Rak M., Para G.
values above 3 [25], thus the positively charged zirconia
binder particles can be readily deposited. In order to
produce zirconia particle monolayers on mica a diluted
sample of the binder (weight content ca 0.0001 % ) was
used. The deposition experiments were carried out under
the diffusion-controlled condition in a thermostatted
cell (for the ionic strength of 10-2 M NaCl). The mica
sheets were placed vertically in order to avoid deposition
of larger aggregates. After a desired time the sheets
were dried and inspected under AFM. A micrograph
of the zirconia particle monolayer obtained in these
measurements is shown in Figure 2. The particle size
distribution was determined as described above by
counting the diameters of approx. 100 particles. The
average particle size determined in these experiments
was 14 nm. As can be deduced the agreement with the
previous value obtained from DLS is quite satisfactory.
This unequivocally suggests that the real size of particles
in the suspension was much larger than the postulated
Figure 2. A micrograph of zirconia particle monolayer de-
posited on mica surface (AFM, semi-contact mode, scan size
5×5 micrometers).
Table 1. Physicochemical data for the zirconia binder.
Property Volume and Unit Remarks
Average particle size in suspension 13 (+/-3) (nm) Malvern DLS by Intensity (I = 10-2 M NaCl, pH = 4.1 )
Zeta potential ζ 26 (+/-2) (mV) Microelectroforesis, (I = 10-2 M NaCl, pH = 4.1)
Density 1.26 g/cm3
Dynamic viscosity 4.87 (mPas)
Surface tension 55 mN m-1
Contact angle 94° stock suspension, paraffin/air, sessile drop method, T = 293 K
Apparent particle density ρ*a 2.0 g cm-3
Particle density ρc 5.1 g cm-3
Residue solid weight wc 0.2
Solid weight content wp 0.33
4 Ceramics – Silikáty 56 (1) 1-8 (2012)
size, probably because of the formation of a shell
on particles, composed of gel layer, which stabilizes
the particle. This hypothesis is supported by the fact
that the binder suspensions were stable over a month
period, which was checked by systematic hydrodynamic
radius measurements carried out as a function of time.
This would be not the case if the particles were charge
stabilized, because of their small size. It can be easily
shown using the classical colloid stability DLVO theory
[19] that for this relatively low zeta potential value
and high concentration, the binder suspension should
aggregate rapidly.
The density and dynamic
viscosity measurements
In order to study the structure of the particles in
the suspension, additional experiments aimed at deter-
mining their density were carried out in addition to the
dynamic viscosity measurements. As shown in Ref. 11,
dynamic viscosity measurements can be utilized to de-
termine the effective hydrodynamic volume of particles
in the suspension and to reveal the presence of a gel shell
and its porosity.
The first step in these measurements involved de-
termining the suspension and particle density. The den-
sity of the stock binder suspension ρsus was routinely de-
termined by the densitometer and was equal to 1.26 g cm-3
which was in accordance with the manufacturer’s data.
However, determining the particle density in the sus-
pension was more complicated. Here, we effectively
applied the suspension dilution method which was used
before [11] in the case of colloid silica binders. The
application of this procedure requires the knowledge
of the solid weight content in the binder suspension.
This was done in the usual way by roasting the sample
under a programmed temperature. It was found that for
the drying temperature of 473 K the solid residue after
24 hours was wp = 0.33 of the initial mass of the sample.
For increased temperature above 573 K, the weight loss
was much higher, so the solid residue was wc = 0.2,
stock suspension pH = 3.5
stock suspension pH = 3.5, T = 293 K
stock suspension, pendant drop method, T = 293 K
dilution method
roasting T > 573 K
T > 573 K
T < 473 K
 Colloid zirconia binder of improved wetting properties

which agrees with the manufacturer data for the zirconia
binder. Thus, the latter value describes the true content
of the solid zirconia in the sample forming the particle
core whereas the former value characterizes the content
of organic complexes forming the shell layer. The ratio
of the two weight contents equals to 1.65.
The density of the solid zirconia core was deter-
mined by the pycnometer using the powder roasted at
a temperature above 573 K. In this way, it was measured
that ρc = 5.1 g cm-3, which is slightly smaller than the
crystalline zirconia equal to 5.79 g cm-3 [7], indicating
that there was some degree of porosity in the solid
zirconia core.
Additionally, knowing the solid weight content wp
and applying the dilution method [11] the apparent
density of particles in the suspension ρ*a was determined
to be 2.0 g cm-3, which is much smaller than the density
of the crystalline zirconia. This indicates that a shell of
low density was present on the particle core. The extent
of the shell layer was further studied using dynamic
viscosity measurements carried out for various dilution
degree. The results of these measurements are collected
in Table 2 and shown graphically in Figure 3 as the
dependence of the reduced viscosity η‾ = (η/ηs) – 1 on the
volume fraction of the core particles [11] Φv = (wc·ρsus)/ρc,
4
3 where ρs is the density of the shell forming complexes.
2 values were previously obtained for the colloid silica
η
where η is the viscosity of the electrolyte and ηs is the
viscosity of the suspension. Using these data, the in-
trinsic viscosity of the suspension can be calculated as
[η] = η‾ /Φv. As can be noticed (see Table 2) the value
of [η] in the limit of very diluted suspension equals
27. Thus, the ratio of this value to the Einstein value,
pertinent to solid spherical particles, equals Vp/Vc, where
Vp is the hydrodynamic particle volume, Vc is the core
volume, equals to 27/2.5 = 10.8. As discussed in Ref.
11 this ratio characterizes the effective hydrodynamic
volume of the composite core/shell particle to the core
volume. Accordingly, the hydrodynamic volume of the
shell is 9.8 times larger than the solid zirconia core.
Knowing the Vp/Vc parameter and the size of the
particle dp, one can easily determine the diameter of the
solid zirconia core from the formula:
1
V 3
dc = d p · c (4)
Vp
Using our data, i.e. dp = 13 nm one can calculate
that dc = 5.9 nm and the hydrodynamic thickness of the
shell to be ds = 3.5 nm. Additionally, knowing the wp/wc
ratio determined as above one can calculate that the appa-
rent density of the shell layer ρ*s equal to 0.34 g cm-3.
Using this value one can further calculate the porosity of
this layer p from the formula:
ρ s∗
p = 1− (5)
ρs
Using our data and assuming ρs = 1.1 g cm-3 one
obtains p = 0.69. It should be noted that very similar

binder [11].
Knowing the porosity one can calculate the apparent
1 density of the composite particle in the solution form the
formula:
V
ρ p + ρ s∗ s
0 V p
0 0.01 0.02 0.03 0.04 0.05 0.06 ρ a∗ = (6)
Vs
ФV 1 + (1 − p )
Vp
Figure
_ 3. The dependence of reduced dynamic viscosity
η = η/ηs - 1 on the volume fraction of the zirconia binder Thus, in our case one obtains from Equation (6) ρa*=
suspension determined at T = 293 K. = 2.09 g cm-3, which is in agreement with the previously

Table 2. Dynamic viscosity of ZrO2 suspensions T = 293 K, ρp = 5.1 g cm-3, intrinsic viscosity.
Nominal weight Density Volume Dynamic viscosity η (η/ηs) – 1
fraction wp ρs (g cm-3) fraction Φv ηs (mPas) ηs [η ] = Φv
0.00 1.0001 0 1.04 1 0
0.02 1.0269 0.00403 1.15 1.108 27
0.05 1.0587 0.0104 1.35 1.299 29
0.1 1.1373 0.0223 1.89 1.816 37
0.12 1.1597 0.0273 2.16 2.073 39
0.15 1.1780 0.0346 3.07 2.943 56
0.20 1.2616 0.0495 4.87 4.660 74

Ceramics – Silikáty 56 (1) 1-8 (2012) 5

 Morga M., Adamczyk Z., Jaszczółt K., Nattich-Rak M., Para G.

mentioned value of 2.0 g cm-3 determined by the dilution
method. Exploiting these experimental findings the com-
posite zirconia binder particles having the core/shell
structure can be schematically represented as shown
in Figure 4. Such a model is in agreement with all the
above reported experimental measurements, explaining
also the high stability of the zirconia binder as due to the
steric repulsion of the shell layers.
which would be suitable for practical applications.
First, surface tension of pure surfactant solutions was
determined. In order to increase the precision of these
measurements, the surface tension dependence on time
was determined for each surfactant solution. Then, these
results were extrapolated to infinite time as was done in
Ref. 17, in order to produce equilibrium values of the
surface tension.
As can be deduced from the results shown
in Figure 5, the fluorinated surfactants studied in
this work effectively reduce the surface tension of
zirconia dispersions. In order to verify this hypothesis,
the surface tension γ of zirconia dispersion in the presence
of the surfactants and their mixtures was determined as
a function of surfactant concentration c.

80

70 1

60

50
γ (mN/m)

2
40

30

20 3

10
0
10-6 10-5 10-4 10-3 10-2
c (mol/dm3)
Figure 4. The schematic representation of the composite core/
Figure 5. The dependence of the surface tension γ on the mo-
/shell zirconia particle.
lar concentration of aqueous solutions of various surfactants:
1 - PFNA (drop shape and the ring method), 2 - Rokafenol N8,
3 - Zonyl FSO.
Modifications of zirconia dispersion
- the surface tension measurements
The surface tension and contact angles for the un-
modified zirconia sol were measured. The stock colloidal 80
zirconia exhibited the surface tension of 55 mN m-1 70
(dyn cm-1). This indicates that the zirconia dispersion
60
contained surfactants, producing a reduction in the
surface tension in comparison to distilled water, which 50
γ (mN/m)

exibits a surface tension of 72.4 mN m-1.

40 1
The contact angle of the colloidal zirconia drop
on the paraffin surface was 94° (see Table 1). This high 30 2
value indicates poor wetting of hydrophobic surfaces
20
being, therefore, unacceptable from the point of view of 3 4
the investment casting industry. 10
These facts indicate unequivocally that modifica- 0
tions of zirconia suspension, by the addition of surfac- 10-6 10-5 10-4 10-3 10-2
tants, are needed in order to produce a binder suitable c (mol/dm3)
for practical applications.
Figure 6. The dependence of the surface tension of zirconia
Therefore, surface tension measurements were per- binder suspensions on the molar concentration of various sur-
formed for the surfactants used in this work with the factants: 1 - Rokafenol N8, 2 - PFNA, 3 - Zonyl FSO, 4 - mix-
aim of determining the range of their concentrations ture (Zonyl FSO + Rokafenol 1:1).

6 Ceramics – Silikáty 56 (1) 1-8 (2012)

 Colloid zirconia binder of improved wetting properties
The results of these measurements are shown in
Figure 6 in the form of the dependence of the equilibrium
surface tension on the surfactant concentration varied
within the range 10-6 to 10-2 M. As can be noticed, all three
surfactants used in the research exhibited a similar trend
in lowering the surface tension in the presence of colloidal
zirconia. The significant difference in the surface activity
of the surfactants occurred at the surfactant concentration
above 3×10-5 M. At the surfactant concentration ranging
from +10-6 M – 3×10-5 M, all three surfactants lowered
the surface tension from 55 mN m-1 to the value of
35 mN m-1. Starting from the concentration of 3×10-5 M
the adsorption of the surfactants at the liquid/air inter-
face exhibits differences in activity of the surfactants.
In the case of the nonionic surfactant, Rokafenol, for
a higher concentration than 3×10-5 M, the surface ten-
sion remains practically constant, reaching the value of
34 mN m-1. The concentration at which this transition
occurs is referred to in the literature as the critical
micelle concentration (c.m.c.) [23,24]. As can be noti-
ced, the PFNA exhibited the higher surface activity than
Rokafenol. The PFNA lowered the surface tension to
the value of 32 mN m-1 – 26 mN m-1 at the surfactant
concentration of 6×10-5 M - 1.5×10-4 M respectively,
achieving the c.m.c. values for c = 3×10-4 M and
lowering the surface tension to the value of 25 mN m-1.
The most significant results were obtained for the non-
ionic surfactant Zonyl-FSO. In this case the surface
tension attained the values of 30mN/m – 23 mN/m for
the concentration range of 4×10-5 M – 8×10-5 M. Even
more significant is the appearance of the c.m.c. for
bulk Zonyl concentration as low as 1.4×10-4 M above
which the equilibrium surface tension of colloid zirconia
attained the value of 21 mN m-1.
It is interesting to mention that the surface activity
of the Zonyl FSO and Rokafenol mixture was also
investigated. The mixture was prepared for the same
140
120
100
1 for concentrations 1×10-4 M, 4×10-4 M and 1×10-3 M,
contact angle (°)
80
2 on the time are plotted. As can be noticed, the initial
3 contact angles were relatively high, equal to 62°, 55°
60
40
4 c = 10-4 M and 4×10-4 M , for a time of 600 seconds.
20
0 quasi-stationary value was 33° for a time of 300 seconds.
10-6 10-5 10-4 10-3
c (mol/dm3)
Figure 7. The dependence of the contact angle of the zirconia
binder of the paraffin/air interface on the concentration of va-
rious surfactants: 1 - PFNA, 2 - Zonyl FSO, 3 - Rokafenol N8,
4 - mixture (Zonyl + Rokafenol N8 1:1).
Ceramics – Silikáty 56 (1) 1-8 (2012)
molar concentration of surfactants c = 1×10-3 M. How-
ever no significant changes in decreased the surface
tension were noticed (see Figure 6).
Modifications of zirconia dispersion
- the contact angle measurement
Surface tension measurements discussed above
provide one with general information, enabling pre-
selection of the most favorable conditions for promoting
an efficient wetting of surfaces by silica dispersions.
However, a precise selection of these parameters
becomes feasible only upon determining the contact
angles of colloidal zirconia drops on the paraffin surface.
In Figure 7 the dependence of the equilibrium
contact angle of the zirconia dispersion is plotted vs. the
surfactant concentration. Taking into account the ability
to decrease contact angles by a pure surfactant, it can
be noticed that for the low concentration range 10-6 M
till 10-4 M, the Rokafenol surfactant was the most effi-
cient in the reduction of the contact angle to the limiting
value of about 45°.
For this concentration range the PFNA and Zonyl
were less effective, probably because of their significant
adsorption on the paraffin surface. The PFNA also was
not efficient in lowering the value of contact angles
which attained 75° for the cb = 2×10-3 M. However, the
Zonyl surfactant at higher concentrations, exceeding 10-4
M, induced a more significant decrease in the contact
angle than Rokafenol, down to a value of about 33°.
Similarly as in the case of surface tension, the
contact angle of the mixture of Zonyl + Rokafenol was
investigated. However, the reduction in the contact angle
was not more efficient than in the case of pure Zonyl
surfactant (see Figure 7).
In such wetting studies, an interesting question of
practical significance is the kinetics of the contact angle
variations as a function of the time. Experiments of this
type, involving zirconia binders, have not been done
before in the literature.
In Figure 8 the dependencies of the contact angle
of the zirconia dispersion modified by addition of Zonyl,
and 53°. However, they decreased with time, attaining
quasi-stationary values equal to 39° and 35° for the
In the case of the highest concentration c = 10-3 M, the
10-2 Hence, these measurements proved unequivocally
that the surfactants studied in our work and their
mixtures can be used for major improvements of wetting
properties of colloid zirconia binder used in investment
casting.
7
 Morga M., Adamczyk Z., Jaszczółt K., Nattich-Rak M., Para G.
Conclusions
An efficient method for quantitatively characterizing
wetting properties of zirconia binders was developed,
based on precise measurements of surface tension and
the dynamic contact angles using the drop shape analysis.
In this way an optimum composition and concentration
range of surfactants were specified, enabling essential
improvements of wetting properties of binders used in
investment casting.
70
65
60
Contact angle (°)
55
50
45 1
40
2 12. Morga M., Para G., Adamczyk Z., Karwiński A.: Ind. Eng.
35
3 Chem. Res. 49, 8532 (2010).
30
25
0 100 200 300 400 500 600
Time (s)
Figure 8. The kinetics of contact angle changes of the zirconia
binder on the paraffin/air interface: 1 - ZrO2 + Zonyl at the con-
centration of 1×10-4 M, 2 - ZrO2 + Zonyl at the concentration
of 4×10-4 M, 3 - ZrO2 + Zonyl at the concentration of 1×10-3 M
Our investigations showed that the fluorinated nonionic
surfactant Zonyl-FSO and its mixture with Rokafenol
effectively reduced the surface tension of colloid zirconia
used as a binder in investment casting to the low value
of 20 mN m-1. Because of surfactant adsorption, the
dynamic contact angle of binders on paraffin films was
decreased, attaining the minimum value of 30° at the bulk
surfactant concentration of about 10-3 M (0.07%). Such
low contact angles represent an essential improvement
in comparison with ordinary binders commonly used
for producing casting forms in the investment casting
industry.
Acknowledgments
This work was supported by the National Centre
for Research and Development (NCBiR) grant:
POIG.01.01.02-12-028/09.
References
1. Kolen’ko Yu.V., Maximov V.D., Burukhin A.A., Muhanov
V.A., Churagulov B.R.: Mater.Sci.Eng. C. 23, 1033 (2003).
2. Arantes T.M., Mambrini G.P., Stroppa D.G., Leite E.R.,
Longo E.: J. Nanopart. Res. 12, 3105 (2010).
3. Zhao N., Pan D., Nie W., Ji X.: J. Am. Chem. Soc. 128,
8 Ceramics – Silikáty 56 (1) 1-8 (2012)
View publication stats
10118 (2006).
4. Clifford Y.T., Bor-Yuan H., Hsien-Yi Ch.: Colloids Surf.,
A: Physicochem. Eng. 237, 105 (2004).
5. Adamczyk Z., Karwiński A., Para G.: Charakterystyka
fizyko-chemiczna spoiw i ciekłych mas ceramicznych stoso-
wanych w odlewnictwie, Instytut Odlewnictwa, Kraków
1999.
6. Adamczyk Z., Siwek B., Zembala M.: Bulletin of the
Polish Academy of Sciences Chemistry. 48, 231( 2000).
7. Jachimska B., Adamczyk Z.: J. Eur. Ceram. Sci. 27, 2209
(2007).
8. Liu D.M.: Ceram. Int. 26, 279 (2000).
9. Baklouti S.M., Romdhane R.B., Boufi Pagnoux S.C., Char-
tiel T., and Baumard J.F.: J. Eur. Ceram. Sci. 23, 905 (2003).
10. Ewais E., Zaman A.A., and Sigmund, W.: J. Eur. Ceram.
Sci. 22, 2805 (2002).
11. Adamczyk Z., Jachimska B., Kollasińska M.: J. Colloid
Interface Sci. 273, 668 (2004).
13. Adamczyk Z., Jachimska B., Kolasińska M., Karwiński,
A.:Bulletin of the Polish Academy of Sciences Chemistry
700
51, 25 (2003).
14. LeBeaua J.M., Boonyongmaneerat Y.: Mater.Sci.Eng., A
458, 17 (2007).
15. Adamczyk Z., Para G., Karwiński A.: Tenside Surf. Det.
38, 261 (1998).
16. Para G., Jarek E., Warszyński P., Adamczyk Z.: Colloids
Surf., A. 222, 213 (2003).
17. Para G., Jarek, E., Warszyński P.: Adv. Colloid Interface
Sci. 122, 39 (2006).
18. Adamczyk Z.: Particles at Interfaces, Interactions,
Deposition, Structure, p 214-219, Elsevier, Academic
Press, Amsterdam 2006.
19. Adamczyk Z., Sadlej K., Wajnryb E., Nattich M., Ekiel-
Jeżewska M.L., Bławzdziewicz J.: Adv. Colloid Interface
Sci. 153, 1 (2010).
20. Hunter R.J.: Zeta Potential in Colloid Science, Academic
Press, London 1981.
21. Delgado A.V., Gonzales-Caballero F., Hunter R.J., Koopal
L. K., Lyklema J.: J. Colloid Interface Sci. 309, 194 (2007).
22. Elimelech M., Gregory J., Jia X., Williams R.: Particle
Deposition and Aggregation: Measurement, Modelling and
Simulation, Butterworth-Heinemann, Oxford 1995.
23. Adamson, A. W.: Physical Chemistry of Surfaces, John
Wiley and Sons, Inc., New York 1990.
24. Miller C.A., Neogi P. Interfacial Phenomena, M. Dekker
Inc., New York 1985.
25. Adamczyk Z., Nattich M., Wasilewska M., Zaucha M. Adv.
Colloid Interface Sci. 168, 3 (2011).